CN102651490B - A kind of renovation process of anode active material of waste lithium battery - Google Patents
A kind of renovation process of anode active material of waste lithium battery Download PDFInfo
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- CN102651490B CN102651490B CN201110046651.0A CN201110046651A CN102651490B CN 102651490 B CN102651490 B CN 102651490B CN 201110046651 A CN201110046651 A CN 201110046651A CN 102651490 B CN102651490 B CN 102651490B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a kind of renovation process of anode active material of waste lithium battery.This renovation process comprises a, gets old positive plate, and described old positive plate comprises plus plate current-collecting body and is attached to the old positive pole material of anode collection surface; Old positive pole material is isolated from old positive plate; B, old positive pole material to be heat-treated, obtain old positive electrode active materials; C, in old positive electrode active materials, add lithium compound, obtain positive electrode active materials mixture; D, by the roasting in oxidizing atmosphere of positive electrode active materials mixture, then to lower the temperature, pulverize; E, spend deionized water pulverize after positive electrode active materials mixture, until the pH of deionized water after washing is 7-9, then dry, obtain the positive electrode active materials regenerated.
Description
Technical field
The present invention relates to a kind of renovation process of refuse battery positive electrode active materials, particularly relate to a kind of renovation process of anode active material of waste lithium battery.
Background technology
Lithium ion battery is a kind of Green Chemistry power supply, has that voltage is high, energy density is large, lightweight, the advantage such as have extended cycle life, be widely used in the various portable set such as mobile phone, notebook computer.
In recent years, because these product development in recent years are swift and violent, therefore, the consumption of lithium ion battery also constantly increases.The thing followed is the appearance of a large amount of used Li ion cells, and these used Li ion cells undoubtedly can to environment without dealing carefully with.In addition, employ cobalt in a large number in lithium ion battery, and cobalt belongs to scarce resource, expensive raw material price, production cost is high, therefore, if directly abandoned by used Li ion cell, can cause the wasting of resources.
In the recovery method of existing used Li ion cell, have directly by battery crushing, then by acid dissolve, then reclaimed the method for various metallic element by the method for chemical precipitation, or the method by roasting after fragmentation reclaims metal material.This method is not owing to being separated battery each several part, and therefore various composition kind more complicated in processing procedure, in subsequent recovery process, step is more.
Such as, CN101054631A discloses a kind of recovery method of valuable metal from disabled lithium ion cell, it is characterized in that comprising the following steps: on disabled lithium ion cell shell, decompress(ion) is carried out in perforation; Disabled lithium ion cell after perforation is put into electrolyte and carries out discharge process; Lithium ion battery after discharge process is carried out calcination process; Lithium ion battery after roasting is carried out fragmentation; Lithium ion battery after fragmentation is carried out magnetic separation; Magnetic Materials and nonmagnetics are carried out classification.Wherein, described electrolyte is a kind of electrolyte solution be selected from sodium chloride, NaOH, sodium sulphate, and the weight percent concentration of electrolyte solution is 0.2-5%.The method needs to carry out the technique such as roasting and perforation, complex steps, and energy consumption is large.
In addition, also have in prior art and first battery each several part is separated, and then the method reclaimed respectively as required.But, generally, inside lithium ion cell close structure, bad by the method separating effect of routine, be separated cost higher, be unfavorable for that industrialization is reclaimed.
Such as, CN1747224A discloses a kind of lithium ion battery from scrapping and reclaims preparation Li
xcoO
2method, X=0.95-1.05 in formula, is characterized in that comprising the following steps: cut open in water by battery, makes positive plate and other isolation of components, and positive plate is cut into fractionlet; With METHYLPYRROLIDONE by positive electrode from wash-out aluminium foil, take out aluminium foil and filter obtain black powder; Then with nitric acid or this black powder of dissolving with hydrochloric acid, filter and obtain containing Co
2+, Li
+nitrate solution or chloride solution; Co is contained again at this
2+, Li
+nitrate solution or chloride solution add ammoniacal liquor, formed blue precipitate; Simultaneously by adding lithium in lithium hydroxide adjustment suspension and the mol ratio of cobalt; Finally, by the sediment filtration in suspension, drying, at 600-900 DEG C, roasting 7-12 hour obtains Li
xcoO
2powder.The method, when being separated positive electrode, needs by cutting, complex operation.Further, the positive electrode active materials high-temperature behavior that obtains of existing various recovery method and security performance lower.
Summary of the invention
Poor in order to overcome the positive electrode high-temperature behavior that recovery method of the prior art obtains, the problem that security performance is low, the invention provides a kind of renovation process of anode active material of waste lithium battery, the positive electrode active materials regenerated by the method has higher security performance and good high-temperature behavior, and battery capacity and good cycle.
The renovation process of anode active material of waste lithium battery disclosed by the invention, comprising:
A, get old positive plate, described old positive plate comprises plus plate current-collecting body and is attached to the old positive pole material of anode collection surface; Old positive pole material is isolated from old positive plate;
B, old positive pole material to be heat-treated, obtain old positive electrode active materials;
C, in old positive electrode active materials, add lithium compound, obtain positive electrode active materials mixture;
D, by the roasting in oxidizing atmosphere of positive electrode active materials mixture, then to lower the temperature, pulverize;
E, spend deionized water pulverize after positive electrode active materials mixture, until the pH of deionized water after washing is 7-9, then dry, obtain the positive electrode active materials regenerated.
In the present invention, positive electrode active materials mixture after pulverizing by adopting deionized water washing, the foreign ion that lithium compound is brought into is added in removing, thus the positive electrode active materials of regeneration can be reused, and its high-temperature behavior and security performance are better, battery capacity and cycle performance excellence.In addition, the method technique is simple, and be applicable to industrialization large-scale production, cost is low, pollution-free, remarkable in economical benefits.And with the material manufacturing lithium ion secondary battery positive electrode, there is identical structure with the positive electrode active materials of the method regeneration, homogeneity of product is high.
Accompanying drawing explanation
Fig. 1 is the XRD figure that the embodiment of the present invention 3 regenerates the positive electrode active materials S3 obtained.
Fig. 2 is LiCoO of the prior art
2xRD figure.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The renovation process of anode active material of waste lithium battery disclosed by the invention, comprising:
A, get old positive plate, described old positive plate comprises plus plate current-collecting body and is attached to the old positive pole material of anode collection surface; Old positive pole material is isolated from old positive plate;
B, old positive pole material to be heat-treated, obtain old positive electrode active materials;
C, in old positive electrode active materials, add lithium compound, obtain positive electrode active materials mixture;
D, by the roasting in oxidizing atmosphere of positive electrode active materials mixture, then to lower the temperature, pulverize;
E, spend deionized water pulverize after positive electrode active materials mixture, until the pH of deionized water after washing is 7-9, then dry, obtain the positive electrode active materials regenerated.
The old positive plate adopted in said method can obtain from waste and old lithium ion battery.The method that old positive plate is separated from waste and old lithium ion battery is comprised waste and old lithium ion battery is soaked in electrolyte aqueous solution, then battery case is peelled off, be separated with old negative plate by old positive plate, in described electrolyte aqueous solution, electrolytical content is 10-50wt%.The present invention can make battery fully discharge by soaking old and useless battery with this electrolyte aqueous solution, the old positive plate of battery and the contact position of old negative plate can be made in addition to produce breach, thus easily can peel off battery case, and be separated by old positive plate.The above-mentioned method isolating old positive plate is known in those skilled in the art, such as, under normal circumstances, can be different with the material of negative plate collector (being generally copper) according to positive plate collector (being generally aluminium), differentiation can be carried out according to color and be separated.The old positive plate separated comprises plus plate current-collecting body and is attached to the old positive pole material of anode collection surface.
In order to shorten soak time, improve and soak efficiency, in described electrolyte aqueous solution, electrolytical content is preferably 20-50wt%.
As long as the time that the consumption of described electrolyte aqueous solution and described waste and old lithium ion battery soak in electrolyte aqueous solution makes waste and old lithium ion battery fully to discharge and the contact position of the old positive plate of battery and old negative plate produces breach, those skilled in the art can easily obtain, such as, the consumption of described electrolyte aqueous solution is 1-20 times of waste and old lithium ion battery weight, the time that described waste and old lithium ion battery soaks in electrolyte aqueous solution is more than 1 hour, is preferably 2-5 hour.In addition, the temperature of described immersion can be 10-40 DEG C.
Described electrolyte can be arbitrary electrolyte, is preferably one or more in sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate and potassium nitrate.From the viewpoint of what reduce costs, described electrolyte is more preferably sodium chloride.
In described step a, the method isolating old positive pole material from old positive plate is: first that old positive plate is broken, then soak in separation solvent, and stir, then sieving separating goes out containing old positive pole material and the slurry being separated solvent.
In said method, can adopt existing various method that old positive plate is carried out fragmentation, such as, carry out Mechanical Crushing.After fragmentation, old positive plate need be immersed to be separated in solvent and stir.One or more of described separation solvent selected from ethanol, methyl alcohol, 1-METHYLPYRROLIDONE, DMA, DMF, methyl-sulfoxide, oxolane, acetone; Be preferably 1-METHYLPYRROLIDONE and/or DMA.The time of described immersion can be 2-6h, and temperature can be 60-100 DEG C.
Through above-mentioned immersion treatment, old positive pole material and plus plate current-collecting body are separated, and then through process of sieving, such as, by rotor-vibrating screen or vacuum sieve, removing plus plate current-collecting body, can obtain containing positive pole material and the slurry being separated solvent of haveing been friends in the past.
In described slurry, the content being separated solvent is 40-90wt%, is preferably 50-85wt%.Although sieve in process above-mentioned, separation solvent can be lost, the amount of loss is relative to very little, negligible in this application the amount being separated solvent.
Owing to containing a large amount of separation solvents in slurry, under preferable case, after isolating slurry, also at 50-200 DEG C, drying process can be carried out to slurry, removing separation solvent wherein.
Meanwhile, inventor finds, also containing the material such as iron, nickel in the old positive pole material more than separated, can produce considerable influence to the security performance of battery.In the present invention, under preferable case, after being processed by drying, magnetic force also can be adopted to carry out adsorption treatment to old positive pole material.Such as, adopt magnet to skim over above the old positive pole material placed, by the magnetisable material in old positive pole material, as iron, nickel etc. are separated, make wherein magnetisable material content (including but not limited to Fe, Ni) be less than 1ppm.
According to the present invention, can heat-treat old positive pole material after above-mentioned process.Heat treatment temperature is 300-600 DEG C, and the time is 2-24h, and being preferably heat treatment temperature is 350-550 DEG C, and the time is 6-20h.Above-mentioned heat treatment can directly be carried out in atmosphere.As known to those skilled in the art, when preparing anode material for lithium-ion batteries, usually can be added into conductive agent particle and binding agent, and these materials above-mentioned still can remain in old and useless battery, being separated with old positive pole material.In the present invention, by carrying out above-mentioned heat treatment to old positive pole material, by residual conductive agent particle and binding agent removing, old positive electrode active materials can be obtained.
The object of the method disclosed in the present recycles the material in old and useless battery, can as raw material again for the preparation of anode material for lithium-ion batteries.The same with the existing various positive electrode active materials preparing lithium ion battery used, the old positive electrode active materials in above-mentioned old positive pole material can contain lithium and assistant metal, described assistant metal be selected from nickel, cobalt or manganese one or more.Such as, described old positive electrode active materials is selected from LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2in one or more.But after being through a large amount of chemical reactions, the composition of the various materials in old positive electrode active materials there occurs change.The requirement preparing anode material for lithium-ion batteries is met in order to make it.As method disclosed by the invention, also need to add lithium compound in old positive electrode active materials.
Concrete, in described step c, the method of adding lithium compound is: the content first analyzing lithium and assistant metal in old positive electrode active materials, then lithium compound is added, obtain positive electrode active materials mixture, the addition of described lithium compound makes the relation with contents of lithium and assistant metal in positive electrode active materials mixture meet LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2in one or more.Such as, the relation with contents of lithium and assistant metal in positive electrode active materials mixture can be made to meet LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2in any one lithium and the relation with contents of assistant metal; Also can be LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2in the relation with contents of lithium in multiple mixture and assistant metal.
Usually, the relation with contents of the addition of lithium compound only need make before old positive electrode active materials uses in the relation with contents of lithium and assistant metal in positive electrode active materials mixture and waste lithium cell (positive electrode active materials namely originally in new lithium battery) lithium and assistant metal is identical, gives full play to its performance to make the positive electrode active materials of regeneration.Positive electrode active materials for known lithium battery forms, and directly can add lithium compound according to corresponding relation.And for the waste lithium cell of the unknown, by ICP and XRD, positive electrode active materials is analyzed, interpolation lithium compound corresponding again after determining its composition.Method disclosed by the invention all has good effect to the positive electrode active materials adopted in prior art, for the ease of comparative illustration, all adopts LiCoO in the embodiment of the present invention
2be described.
Wherein, the method analyzing the content of lithium and assistant metal in old positive electrode active materials is well known in the art, such as, chemical analysis or icp analysis method can be adopted to obtain.
According to the present invention, described lithium compound be selected from lithium carbonate, lithium hydroxide, lithia or lithium nitrate one or more.
For the positive electrode active materials mixture obtained, also need to carry out calcination process to it, described roasting is carried out in oxidizing atmosphere, and as what commonly use, above-mentioned calcination process can directly be carried out in atmosphere.Under preferable case, described sintering temperature is 700-1000 DEG C, and the time is 6-24h, and more preferably sintering temperature is 750-950 DEG C, and the time is 8-20h.
By the positive electrode active materials mixture cooling after roasting, pulverize after being cooled to room temperature.Under preferable case, the positive electrode active materials mixture after roasting is crushed to below 200 orders.
Then the positive electrode active materials mixture after adopting deionized water washing to pulverize, until the pH of deionized water after washing is 7-9.Inventor finds, by washing the positive electrode active materials mixture after roasting, improves security performance and the high-temperature behavior of the lithium ion battery prepared by it.
Under preferable case, also need to dry the positive electrode active materials mixture after water washed, the temperature of described oven dry is 200-400 DEG C.
By processing the positive electrode active materials that can obtain regenerating above.The positive electrode active materials of this regeneration can directly use, and prepares lithium ion battery.
Below by embodiment, the present invention is further detailed.
Embodiment 1
The present embodiment is for illustration of the renovation process of anode active material of waste lithium battery disclosed by the invention.
(positive electrode active materials is LiCoO to mobile phone lithium rechargeable battery charge and discharge cycles lost efficacy
2) be soak 2 hours in the sodium-chloride water solution of 10wt% in concentration, the temperature of immersion is 25 DEG C, then peels off battery case, isolate old positive plate, after its mechanical crushing, be placed in ethanol and soak, and carry out mechanical agitation, old positive pole material is separated with plus plate current-collecting body.And then be separated through rotor-vibrating screen, obtain containing positive pole material and the slurry being separated solvent of haveing been friends in the past, wherein, ethanol content is 40wt%.
Above-mentioned slurry is carried out in air atmosphere at 50 DEG C drying process, then toast 10 hours at 600 DEG C, obtain old positive electrode active materials.
Adopt icp analysis method to analyze above-mentioned old positive electrode active materials, then add Li
2cO
3, obtain positive electrode active materials mixture, wherein, the mol ratio of lithium and cobalt is 1:1.
By positive electrode active materials mixture in atmosphere, roasting 20h at 750 DEG C.Then cooling down, is crushed to 200 orders and sieves.
Positive electrode active materials mixture after adopting deionized water washing to pulverize, until the pH of deionized water after washing is 7, then at 200 DEG C, baking obtains the positive electrode active materials S1 regenerated for 8 hours.
Embodiment 2
The present embodiment is for illustration of the renovation process of anode active material of waste lithium battery disclosed by the invention.
(positive electrode active materials is LiCoO to mobile phone lithium rechargeable battery charge and discharge cycles lost efficacy
2) be soak 3 hours in the sodium-chloride water solution of 15wt% in concentration, the temperature of immersion is 15 DEG C, then peels off battery case, isolate old positive plate, after its mechanical crushing, be placed in acetone and soak, and carry out mechanical agitation, old positive pole material is separated with plus plate current-collecting body.And then be separated through rotor-vibrating screen, obtain containing positive pole material and the slurry being separated solvent of haveing been friends in the past, wherein, content of acetone is 90wt%.
Above-mentioned slurry is carried out in air atmosphere at 200 DEG C drying process, then heat treatment 15 hours at 300 DEG C, obtains old positive electrode active materials.
Adopt icp analysis method to analyze above-mentioned old positive electrode active materials, then add lithia, obtain positive electrode active materials mixture, wherein, the mol ratio of lithium and cobalt is 1:1.
By positive electrode active materials mixture in atmosphere, roasting 6h at 950 DEG C.Then cooling down, is crushed to 200 orders and sieves.
Positive electrode active materials mixture after adopting deionized water washing to pulverize, until the pH of deionized water after washing is 8, then at 400 DEG C, baking obtains the positive electrode active materials S2 regenerated for 5 hours.
Embodiment 3
The present embodiment is for illustration of the renovation process of anode active material of waste lithium battery disclosed by the invention.
(positive electrode active materials is LiCoO to mobile phone lithium rechargeable battery charge and discharge cycles lost efficacy
2) be soak 3 hours in the sodium-chloride water solution of 20wt% in concentration, the temperature of immersion is 20 DEG C, then peels off battery case, isolate old positive plate, after its mechanical crushing, be placed in 1-METHYLPYRROLIDONE and soak, and carry out mechanical agitation, old positive pole material is separated with plus plate current-collecting body.And then be separated through rotor-vibrating screen, obtain containing positive pole material and the slurry being separated solvent of haveing been friends in the past, wherein, 1-METHYLPYRROLIDONE content is 60wt%.
Above-mentioned slurry is carried out in air atmosphere at 50 DEG C drying process, then adopt magnetic force to carry out adsorption treatment to old positive pole material, then toast 10 hours at 500 DEG C, obtain old positive electrode active materials.
Adopt icp analysis method to analyze above-mentioned old positive electrode active materials, then add lithium hydroxide, obtain positive electrode active materials mixture, wherein, the mol ratio of lithium and cobalt is 1:1.
By positive electrode active materials mixture in atmosphere, roasting 10h at 800 DEG C.Then cooling down, is crushed to 200 orders and sieves.
Positive electrode active materials mixture after adopting deionized water washing to pulverize, until the pH of deionized water after washing is 8, then at 300 DEG C, baking obtains the positive electrode active materials S3 regenerated for 8 hours.
Embodiment 4
The present embodiment is for illustration of the renovation process of anode active material of waste lithium battery disclosed by the invention.
(positive electrode active materials is LiCoO to mobile phone lithium rechargeable battery charge and discharge cycles lost efficacy
2) be soak 2 hours in the sodium-chloride water solution of 30wt% in concentration, the temperature of immersion is 40 DEG C, then peels off battery case, isolate old positive plate, after its mechanical crushing, be placed in 1-METHYLPYRROLIDONE and soak, and carry out mechanical agitation, old positive pole material is separated with plus plate current-collecting body.And then be separated through rotor-vibrating screen, obtain containing positive pole material and the slurry being separated solvent of haveing been friends in the past, wherein, 1-METHYLPYRROLIDONE content is 70wt%.
Above-mentioned slurry is carried out in air atmosphere at 150 DEG C drying process, then adopt magnetic force to carry out adsorption treatment to old positive pole material, then toast 10 hours at 400 DEG C, obtain old positive electrode active materials.
Adopt icp analysis method to analyze above-mentioned old positive electrode active materials, then add lithium hydroxide, obtain positive electrode active materials mixture, wherein, the mol ratio of lithium and cobalt is 1:1.
By positive electrode active materials mixture in atmosphere, roasting 8h at 850 DEG C.Then cooling down, is crushed to 200 orders and sieves.
Positive electrode active materials mixture after adopting deionized water washing to pulverize, until the pH of deionized water after washing is 9, then at 300 DEG C, baking obtains the positive electrode active materials S4 regenerated for 8 hours.
Comparative example 1
This comparative example is for illustration of the renovation process of anode active material of waste lithium battery of the prior art.
The renovation process of positive electrode active materials is substantially the same manner as Example 1, unlike, do not adopt deionized water to wash the positive electrode active materials mixture after pulverizing, obtain the positive electrode active materials D1 regenerated.
Performance test
1, XRD test
Adopt the D/MAX2200PC type x-ray powder diffraction instrument of Rigaku to the positive electrode active materials S3 of regeneration and the LiCoO be commercially available
2carry out XRD test.Fig. 1 is shown in by the XRD collection of illustrative plates of the S3 obtained, the LiCoO be commercially available
2xRD collection of illustrative plates see Fig. 2.
As can be seen from Fig. 1 and Fig. 2, the positive electrode active materials S3 regenerated by method disclosed by the invention and commercially available LiCoO
2structure the same, can be used as positive electrode active materials completely and reuse.
The preparation of test battery:
Adopt the positive electrode active materials of each embodiment and comparative example to prepare anode sizing agent respectively, batching mass ratio is positive electrode active materials: conductive carbon black: binding agent PVDF:NMP=100:5:5:110, stirs and form uniform anode sizing agent in de-airing mixer.This anode sizing agent is coated on equably the both sides of aluminium foil, then oven dry at 150 DEG C, roll-in, cuts the obtained positive plate being of a size of 540 × 43.5mm.The quality of the positive electrode active materials on record positive plate.
Adopt native graphite in de-airing mixer, stir obtained uniform cathode size, batching mass ratio is native graphite: conductive agent carbon fiber: binding agent PVDF:NMP=100:3:4:100.This cathode size is coated on equably the both sides of Copper Foil, then oven dry at 150 DEG C, roll-in, cuts the obtained negative plate being of a size of 500 × 44mm.
Respectively above-mentioned positive and negative plate and microporous polypropylene membrane are wound into a rectangular cell pole piece, electrolyte is injected battery aluminum shell with the amount of 3.8g/Ah, sealing, makes lithium rechargeable battery.Wherein electrolyte is that to be dissolved in the concentration formed in ethylene carbonate/divinyl carbonate/dimethyl carbonate=1:1:1 mixed solvent be the solution of 1mol/L to lithium hexafluoro phosphate.
Adopt S1-S4, D1 by said method corresponding prepare lithium battery A1-A4, DA1.
Thickness measuring and volume test are carried out to test battery A1-A4, DA1:
2, thickness measuring
Adopt vernier caliper test lithium battery A1-A4, DA1 original depth at normal temperatures and 85 DEG C of thickness stored after 2h.
Shelve 2h varied in thickness=shelve 2h thickness-original depth
Thickness change=(shelving 2h varied in thickness/original depth) × 100%
The test data obtained inserts table 1
As can be seen from the test result of table 1, the security performance of the lithium ion battery that the positive electrode active materials regenerated by method disclosed by the invention is made is good, and heat resistance is very excellent.
3, volume test
Above-mentioned obtained battery is placed on test cashier's office in a shop respectively, first carries out constant current charge to upper voltage limit 4.2V with 0.5C, then constant voltage charge 2.5h; After shelving 10min, be discharged to 3.0V with the electric current of 0.5C from 4.2V, the discharge capacity first of record battery.Then, after repeating above-mentioned steps 200 times, the discharge capacity after record circulating battery 200 times, calculate 200 circulation volume sustainment rates and initial discharge specific capacity by following formula, acquired results is listed in table 2.
Capacity surplus ratio=(the 200th discharge capacity/discharge capacity first) × 100%
As can be seen from the test result of table 2, the good cycle of the lithium ion battery that the positive electrode active materials regenerated by method disclosed by the invention is made, capacity is high.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a renovation process for anode active material of waste lithium battery, comprising:
A, get old positive plate, described old positive plate comprises plus plate current-collecting body and is attached to the old positive pole material of anode collection surface; Old positive pole material is isolated from old positive plate; Described old positive plate is soaked in electrolyte aqueous solution by waste and old lithium ion battery, then peel off battery case, be separated with old negative plate by old positive plate and obtain; Wherein, in described electrolyte aqueous solution, electrolytical content is 20-50wt%; The method isolating old positive pole material from old positive plate is: first that old positive plate is broken, then soak in separation solvent, and stir, then sieving separating goes out containing old positive pole material and the slurry being separated solvent; After isolating slurry, at 50-200 DEG C, drying process is carried out to slurry; After being processed by drying, magnetic force is adopted to carry out adsorption treatment to old positive pole material;
B, old positive pole material to be heat-treated, obtain old positive electrode active materials;
C, in old positive electrode active materials, add lithium compound, obtain positive electrode active materials mixture;
D, by the roasting in oxidizing atmosphere of positive electrode active materials mixture, then to lower the temperature, pulverize;
E, spend deionized water pulverize after positive electrode active materials mixture, until the pH of deionized water after washing is 7-9, then dry, obtain the positive electrode active materials regenerated.
2. renovation process according to claim 1, is characterized in that, one or more of described separation solvent selected from ethanol, methyl alcohol, 1-METHYLPYRROLIDONE, DMA, DMF, methyl-sulfoxide, oxolane, acetone; In described slurry, the content being separated solvent is 40-90wt%.
3. renovation process according to claim 1, is characterized in that, in described step b, heat treatment temperature is 300-600 DEG C, and the time is 2-24h.
4. renovation process according to claim 1, is characterized in that, containing lithium and assistant metal in described old positive electrode active materials, described assistant metal be selected from nickel, cobalt or manganese one or more; In described step c, first analyze the content of lithium and assistant metal in old positive electrode active materials, then add lithium compound, obtain positive electrode active materials mixture, the addition of described lithium compound makes the relation with contents of lithium and assistant metal in positive electrode active materials mixture meet LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2in one or more.
5. the renovation process according to claim 1 or 4, is characterized in that, described lithium compound be selected from lithium carbonate, lithium hydroxide, lithia or lithium nitrate one or more.
6. renovation process according to claim 1, is characterized in that, in described steps d, sintering temperature is 700-1000 DEG C, and the time is 6-24h.
7. renovation process according to claim 1, is characterized in that, in described steps d, the positive electrode active materials mixture after roasting is crushed to below 200 orders; In described step e, the temperature of described oven dry is 200-400 DEG C.
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| CN104183882B (en) * | 2013-05-27 | 2018-04-27 | 湖南邦普循环科技有限公司 | A kind of method of pole fluid and active material in separation positive electrode plate and negative electrode plate of lithium ion battery |
| CN105244561B (en) * | 2015-08-28 | 2017-09-12 | 郭建 | The method that high voltage multicomponent material is prepared as raw material using waste and old polynary dynamic lithium battery |
| CN105356000A (en) * | 2015-12-10 | 2016-02-24 | 华南师范大学 | Recovering method of LiFePO4 positive electrode in spent lithium-ion battery |
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